where k (M− 2 s− 1) can be determined from the
in the pH range 2 to 5, from 5 to 40 °C and 0.01 to 1 M.The effect of pH and ionic strength on the reaction suggest that the rates are due to
where H2A = H2CrO4, HA = HCrO4, H2B = H2SO3 and HB = HSO3. The overall rate expression over the investigated pH range can be determined from
k=kH2A–H2B(αH2A)(αH2B)2+kHA–H2B(αHA)(αH2B)2+kH2A–HB(αH2A)(αHB)2
with kH2A−H2B = 5.0 × 107, kHA–H2B = 1.5 × 106 and kH2A–HB = 6.7 × 107.Fe(III) in the range 1.5 to 20 μM exerts a small catalytic effect on the reaction and significantly lowers the initial concentration of Cr(VI) compared to the nominal value. Contrary to Fe(III), formaldehyde (20 to 200 μM) reacts with S(IV) to form the hydroxymethanesulfonate adduct (CH2OHSO3), which does not react with Cr(VI). Major cations Mg2+ and some minor elements such as Ba2+ and Cu2+ did not affect the rates. The application of this rate law to environmental conditions suggest that this reaction may have a role in acidic solutions (aerosols and fog droplets). This reaction becomes more important in the presence of high Fe(III) and low HMS concentrations, contributing to affect the atmospheric transport of chromium species and the distribution of redox species of chromium, which reach surface water from atmospheric depositions.  相似文献   
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81.
Most structures are subjected to more cyclic loads during their life time than static loads. These cyclic action could be a result of either natural or man-made activities and may lead to soil failure. In order to understand the response of the foundation and its interaction with these complex cyclic loadings, various researchers have over the years developed different constitutive models. Although a lot of research is being carried out on these relatively new models, little or no details exist in literature about the model-based identification of the cyclic constitutive parameters which to a large extent govern the quality of the model output. This could be attributed to the difficulties and complexities of the inverse modeling of such complex phenomena. A variety of optimisation strategies are available for the solution of the sum of least-squares problems as usually done in the field of model calibration. However, for the back analysis (calibration) of the soil response to oscillatory load functions, this article gives insight into the model calibration challenges and also puts forward a method for the inverse modeling of cyclic loaded foundation response such that high-quality solutions are obtained with minimum computational effort.  相似文献   
82.
The advent in satellite altimetry with the most accurate satellite radar altimeter since 1992 and its successive missions have enabled the routine global monitoring of water-level (or stage) for surface waters and changes in the quantities of dammed water reservoirs. However, satellite altimeter measurements typically have spatial resolution capable of observing only large water bodies, such as major lakes and rivers. This paper addresses the challenges of how to investigate water levels in medium (~?1 km in width) to small (~?100 m and narrower) rivers. Comparisons between the ENVISAT altimetry ICE-1 waveform retracking height and standard water-level measurements for multiple sections of Ohio River, Columbia River, and Red River of the North in the United States (US) reveals that the satellite altimetry measured water levels agree well with those observed at nearby US Geological Survey gaging stations over the 10-year period starting from 2002. The significant results include those obtained at Thompson, North Dakota (ND, correlation coefficient or R value of 0.76 between satellite and in situ water-level measurements) and Fargo, ND (R?=?0.74), where the stream channels of Red River are merely?~?50 m and ~?40 m wide, respectively, under normal climatic conditions. In addition, demonstrations of the approach over largely inaccessible portions of Tigris–Euphrates Rivers and Helmand River in the Middle East aided in understanding hydrology in these systems. This study demonstrates the ability of satellite radar altimetry to characterize rivers in these study regions which are much narrower than 100 m in width.  相似文献   
83.
84.
Garnet crystals with quartz inclusions were hydrothermally crystallized from oxide starting materials in piston–cylinder apparatuses at pressures from 0.5 to 3 GPa and temperatures ranging from 700 to 800 °C to study how entrapment conditions affect remnant pressures of quartz inclusions used for quartz-in-garnet (QuiG) elastic thermobarometry. Systematic changes of the 128, 206 and 464 cm?1 Raman band frequencies of quartz were used to determine pressures of quartz inclusions in garnet using Raman spectroscopy calibrations that describe the P–T dependencies of Raman band shifts for quartz under hydrostatic pressure. Within analytical uncertainties, inclusion pressures calculated for each of the three Raman band frequencies are equivalent, which suggests that non-hydrostatic stress effects caused by elastic anisotropy in quartz are smaller than measurement errors. The experimental quartz inclusions have pressures ranging from ??0.351 to 1.247 GPa that span the range of values observed for quartz inclusions in garnets from natural rocks. Quartz inclusion pressures were used to model P–T conditions at which the inclusions could have been trapped. The accuracy of QuiG thermobarometry was evaluated by considering the differences between pressures measured during experiments and pressures calculated using published equation of state parameters for quartz and garnet. Our experimental results demonstrate that Raman measurements performed at room temperature can be used without corrections to estimate garnet crystallization pressures. Calculated entrapment pressures for quartz inclusions in garnet are less than ~?10% different from pressures measured during the experiments. Because the method is simple to apply with reasonable accuracy, we expect widespread usage of QuiG thermobarometry to estimate crystallization conditions for garnet-bearing silicic rocks.  相似文献   
85.
The occurrence of disasters such as extreme flooding in urban environments has severe consequences, not only on the human population but also on critical infrastructures such as the road networks, which are of vital importance for everyday living and particularly for emergency response. In this article, our main goal is to present-conceptually and in praxis-a model that could be used from the emergency responders for timely and efficient emergency management and response in an urban complex environment. For the city of Cologne in Germany, we aim to indicate possible ways to decrease the emergency response time during an extreme flood scenario through the development of an accessibility indicator, which consists of different components. Therefore, we will investigate the opportunities that occur, in a flood risk scenario, from the use of geographic information in different forms such as Volunteered Geographic Information (VGI) and open-source data in an ArcGIS environment, to increase urban resilience through the decreasing emergency response time. We will focus on network analysis for the fire brigades (first acting emergency responders) during a flood scenario to calculate their emergency response ranges and emergency response routes through flooded road networks, for the assistance of the possibly affected hospitals, refugee homes and fire brigades, which can be flooded. At the end of the paper, we suggest that the vulnerable community of the refugees could be taken into consideration as a new source of VGI, as an additional component that would lead to the decrease in the emergency response time. The geo-located information that could be provided by the refugee community can be very useful in emergency situations, such as those examined in this article where timely information can be forwarded to the proper authorities for a more focused and timely emergency response, increasing the resilience of the urban population and their community.  相似文献   
86.
Loess–palaeosol sequences (LPS) represent important records of palaeoenvironmental dynamics throughout the Quaternary. During the Pleistocene's dry and cold phases, the Danube's riverbed was one of the major sources for loess sediments that built up LPS in southern Germany and southeastern Europe. Surprisingly, studies addressing Bavarian LPS along the Danube River often lack actuality. The Attenfeld site was one of them and is often cited as a typical LPS. Nevertheless, the site's previous interpretations are based on a few empirical data and field observations. Considering the site's closeness to the sediment's source area, the Alps, and the region's importance in Middle and Upper Palaeolithic migrational movements, those former renditions needed an evaluation. Therefore, we applied a multi-proxy approach (including analyses of grain-size distribution, element composition, and sediment colour attributes) combined with optically stimulated luminescence. Based on our findings, we conclude that the Attenfeld site's former interpretations might be too generalised. We identified units that were not mentioned by previous studies (e.g. Early Glacial dark greyish horizon). Field observations, sediment characteristics, and age estimates indicate sediment deposition of the dated units partly before MIS 4, which contrasts with previous interpretations. The results further demonstrate how sensitive LPS are to environmental settings and dynamics.  相似文献   
87.
Upper Permian to Lower Triassic coastal plain successions of the Sydney Basin in eastern Australia have been investigated in outcrop and continuous drillcores. The purpose of the investigation is to provide an assessment of palaeoenvironmental change at high southern palaeolatitudes in a continental margin context for the late Permian (Lopingian), across the end‐Permian Extinction interval, and into the Early Triassic. These basins were affected by explosive volcanic eruptions during the late Permian and, to a much lesser extent, during the Early Triassic, allowing high‐resolution age determination on the numerous tuff horizons. Palaeobotanical and radiogenic isotope data indicate that the end‐Permian Extinction occurs at the top of the uppermost coal bed, and the Permo‐Triassic boundary either within an immediately overlying mudrock succession or within a succeeding channel sandstone body, depending on locality due to lateral variation. Late Permian depositional environments were initially (during the Wuchiapingian) shallow marine and deltaic, but coastal plain fluvial environments with extensive coal‐forming mires became progressively established during the early late Permian, reflected in numerous preserved coal seams. The fluvial style of coastal plain channel deposits varies geographically. However, apart from the loss of peat‐forming mires, no significant long‐term change in depositional style (grain size, sediment‐body architecture, or sediment dispersal direction) was noted across the end‐Permian Extinction (pinpointed by turnover of the palaeoflora). There is no evidence for immediate aridification across the boundary despite a loss of coal from these successions. Rather, the end‐Permian Extinction marks the base of a long‐term, progressive trend towards better‐drained alluvial conditions into the Early Triassic. Indeed, the floral turnover was immediately followed by a flooding event in basinal depocentres, following which fluvial systems similar to those active prior to the end‐Permian Extinction were re‐established. The age of the floral extinction is constrained to 252.54 ± 0.08 to 252.10 ± 0.06 Ma by a suite of new Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry U‐Pb ages on zircon grains. Another new age indicates that the return to fluvial sedimentation similar to that before the end‐Permian Extinction occurred in the basal Triassic (prior to 251.51 ± 0.14 Ma). The character of the surface separating coal‐bearing pre‐end‐Permian Extinction from coal‐barren post‐end‐Permian Extinction strata varies across the basins. In basin‐central locations, the contact varies from disconformable, where a fluvial channel body has cut down to the level of the top coal, to conformable where the top coal is overlain by mudrocks and interbedded sandstone–siltstone facies. In basin‐marginal locations, however, the contact is a pronounced erosional disconformity with coarse‐grained alluvial facies overlying older Permian rocks. There is no evidence that the contact is everywhere a disconformity or unconformity.  相似文献   
88.
We constrain the multistage tectonic evolution of the Palaeoproterozoic UHT metamorphic(P=0.9–1.0 GPa,T>1000℃,t=2088–2031 Ma)Bakhuis Granulite Belt(BGB)in Surinam on the Guiana Shield,using large-to small-scale structures,Al-in-hornblende thermobarometry and published fluid inclusion and zircon geochronological data.The BGB forms a narrow,NE–SW striking belt between two formerly connected,~E–W oriented granite-greenstone belts,formed between converging Amazonian and West African continental masses prior to collision and Transamazonian orogeny.Inherited detrital zircon in BGB metasediments conforms agewise to Birimian zircon of West Africa and suggests derivation from the subsequently subducted African passive margin.Ultrahigh-temperature metamorphism may have followed slab break-off and asthenospheric heat advection.Peak metamorphic structures result from layer-parallel shearing and folding,reflecting initial transtensional exhumation of the subducted African margin after slab break-off.A second HT event involves intrusion,at ca.0.49 GPa,of charnockites and metagabbros at 1993–1984 Ma and a layered anorthosite at 1980 Ma,after the BGB had already cooled to<400℃.The event is related to northward subduction under the greenstone belts,along a new active margin to their south.A pronounced syntaxial bend in the new margin points northward towards the BGB and is likely the result of indentation by an anticlinorial flexural bulge of the subducting plate.Tearing of the subducting oceanic plate along this bulge explains why the charnockites are restricted to the BGB.The BGB subsequently experienced doming under an extensional detachment exposed in its southwestern border zone.Exhumation was focused in the BGB as a result of the flexural bulge in the subducting plate and localised heating of the overriding plate by charnockite magmatism.The present,straight NE–SW long-side boundaries of the BGB are superimposed mylonite zones,overprinted by pseudotachylites,previously dated at ca.1200 Ma and 950 Ma,respectively.The 1200 Ma mylonites reflect transpressional popping-up of the BGB,caused by EW-directed intraplate principal compressive stresses from Grenvillian collision preserved under the eastern Andes.Further exhumation of the BGB involved the 950 Ma pseudotachylite decorated faulting,and Phanerozoic faulting along reactivated Meso-and Neoproterozoic lineaments.  相似文献   
89.
90.
The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔHapp of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression
−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]2
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